Mid-infrared sensor

ABSTRACT

A sensor for monitoring a species which is a component of a fluid. The sensor includes an internal reflection window which, in use, is in direct contact with the fluid. The sensor further includes a mid-infrared light source which directs a beam of mid-infrared radiation into said window for attenuated internal reflection at an interface between the window and the fluid. The sensor further includes a first narrow bandpass filter which preferentially transmits mid-infrared radiation over a band of wavelengths corresponding to an absorbance peak of the species. The sensor further includes an infrared detector which detects filtered mid-infrared radiation transmitted through the first filter and a processor for measuring the intensity of the detected mid-infrared radiation transmitted through the first filter, and determines therefrom an amount of the species in the fluid.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application claims priority as a continuation application of U.S.patent application Ser. No. 15/511,333, filed Mar. 15, 2017, with thesame title. The patent application is incorporated by reference in itsentirety.

BACKGROUND

Embodiments of the present disclosure relate to a mid-infrared sensorfor monitoring a species, which is a component of a fluid.

The analysis of chemical composition of fluid samples from hydrocarbonwells for the determination of phase behaviour and chemical compositionis a critical step in the monitoring and management of a hydrocarbonwell as well as the evaluation of the producibility and economic valueof the hydrocarbon reserves. Similarly, the monitoring of fluidcomposition during production or other operations can have an importantbearing on reservoir management decisions. Similarly, determination ofphase behaviour and chemical composition is important in pipelines andthe like used to convey/transport hydrocarbons from the wellhead,including subsea pipelines.

Several disclosures have described analysis of specific gases inborehole fluids in the downhole environment using near-infrared (e.g.λ=1-2.5 μm) spectral measurements. For example, U.S. Pat. No. 5,859,430describes the use of near-infrared spectroscopy to determinequantitatively the presence of methane, ethane and other simplehydrocarbons in the gas phase. The gases were detected using theabsorption of near-infrared radiation by the overtone/combinationvibrational modes of the molecules in the spectral region 1.64-1.75 μm.

More recently, U.S. Pat. No. 6,995,360 describes the use of mid-infraredradiation with a wavelength λ=3-5 μm to monitor gases in downholeenvironments, and U.S. Pat. Publication No. 2012/0290208 proposes theuse of mid-infrared radiation to monitor sequestered carbon dioxidedissolved into the liquid solutions of saline aquifers.

There are however many technical problems with using mid-infraredsensors in the hydrocarbon industry and processing information from suchsensors. Additionally, much of the utility of mid-infrared spectroscopyhas not previously been recognized.

SUMMARY

Embodiments of the present disclosure are at least partly based on therecognition that species may be monitored/detected using a sensor basedon mid-infrared radiation absorbance. In some embodiments, accuracy ofsuch mid-infrared monitoring ism provided where monitoring temperaturesmay vary and/or may comprise high or low extremes. In other embodiments,mid-infrared spectroscopy may be used to monitor and/or detect speciessuch as acids, hydrate inhibitors and/or the like.

Accordingly, in a first aspect, an embodiment of the present disclosureprovides a sensor for monitoring a species which is a component of afluid. In the embodiment, the sensor includes an internal reflectionwindow for contacting with the fluid, a mid-infrared light source thatdirects a beam of mid-infrared radiation into said window sop that thedirected beam undergoes attenuated internal reflection at an interfacebetween the window and the fluid, a temperature invariant narrowbandpass filter that preferentially transmits mid-infrared radiationover a band of wavelengths corresponding to an absorbance peak of thespecies to filter internally reflected mid-infrared radiation receivedfrom the window, an infrared detector for detecting filteredmid-infrared radiation transmitted through the filter; and a processorfor determining the intensity of the detected mid-infrared radiationtransmitted through the first filter. The detected/measured mid-infraredradiation may be used to determine an amount/concentration of thespecies in the fluid. The temperature invariant narrow bandpass filteris configured such that its wavelength transmission band issubstantially temperature invariant over all temperatures in the rangefrom 25 to 150° C.

Temperatures in downhole environments can vary greatly, e.g. from roomtemperature up to 150° C. or 200° C. In embodiments of the presentdisclosure, by using a temperature invariant filter, it is possible touse a mid-infrared sensor in a downhole environment and obtainaccurate/meaningful measurements.

As discussed below, in embodiments of the present disclosure, the sensormay be part of a sensor arrangement, e.g. with a further similar sensorfor obtaining a reference intensity.

In a second aspect, an embodiment of the present disclosure provides theuse of the sensor, or sensor arrangement, of the first aspect todetermine an amount of a species which is a component of a fluid. Forexample, a method of monitoring a species which is a component of afluid may include: providing the sensor of the first aspect such thatthe internal reflection window is in direct contact with the fluid; andoperating the sensor to determine an amount of the species in the fluid.

In a third aspect, an embodiment of the present disclosure provides awell tool (such as a drilling, production well or wireline samplingtool) including the sensor, or sensor arrangement, of the first aspect.

In a fourth aspect, an embodiment of the present disclosure provides amid-infrared sensor and a method of using such a sensor fordetecting/monitoring particular species, including hydrateinhibitors—such as methanol, ethanol, monoethylene glycol, diethyleneglycol, polyvinylpyrrolidone, polyvinylcaprolactam and/or the like—andmineral acids.

In a fifth aspect, in accordance with an embodiment of the presentdisclosure, a method for monitoring a species that is a component of afluid is provided comprising:

-   -   contacting the fluid with an internal reflection window;    -   directing a beam of mid-infrared radiation into said window to        provide for attenuated internal reflection at an interface        between the window and the fluid;    -   passing the internally reflected mid-infrared radiation from the        window through a first narrow bandpass filter to preferentially        transmit mid-infrared radiation over a band of wavelengths        corresponding to an absorbance peak of the species to filter,        wherein the first narrow bandpass filter is configured to        provide that a wavelength transmission band of the first narrow        bandpass filter is substantially temperature invariant over all        temperatures in the range from about 25 to 150° C.;    -   detecting the filtered mid-infrared radiation transmitted        through the first narrow bandpass filter; and processing an        intensity of the detected mid-infrared radiation transmitted        through the first narrow bandpass filter and an amount of the        species in the fluid.

Optional features of embodiments of the present disclosure will now beset out. These are applicable singly or in any combination with anyaspect of the embodiments of the present disclosure.

The fluid may be a liquid, such as a production fluid, drilling fluid,completion fluid or a servicing fluid. The fluid may be a gas, such as aproduction gas. The fluid may be a liquid/gas mixture.

By “mid-infrared radiation,” it is meant herein that the radiation has awavelength in the range from about 2 to 20 μm, and in some embodimentsfrom about 3 to 12 μm or from about 3 to 10 μm.

To cover a greater range of downhole temperatures, the wavelengthtransmission band of the first narrow bandpass filter may besubstantially temperature invariant over all temperatures in the rangefrom about 25 to 200° C. To cover both downhole and subsea conditions(where ambient temperatures can be in the range from −25 to 25° C.), thewavelength transmission band of the first narrow bandpass filter may besubstantially temperature invariant over all temperatures in the rangefrom about −25 to 125, 150 or 200° C.

By “substantially temperature invariant,” it is meant herein that thevariance is at most about 0.1 nm/° C. In some embodiments, the varianceis at most about 0.05, 0.03, 0.02 or 0.01 nm/° C.

In some embodiments of the present disclosure, the filter may be aninterference filter. For example, the filter may in some embodimentscomprise a substrate, formed of Si, SiO₂, Al₂O₃, Ge, ZnSe and/or thelike and at each opposing side of the substrate alternating high and lowrefractive index layers may be formed. For example, in some embodiments,the high refractive index layers may be formed of PbTe, PbSe, PbS and/orthe like and the low refractive index layers may be formed of ZnS, ZnSeand/or the like.

In some embodiments of the present disclosure, the filter may comprisethree or more half wavelength cavities. Many conventional filtersdisplay high band shifts with increasing temperature. For example,shifts in the range 0.2 to 0.6 nm/° C. are typical. Transmissivities ofconventional filters also tend to reduce with increasing temperature.However, in embodiments of the present disclosure, by using aPbTe-based, PbSe-based, PbS-based and/or the like interference filter,it is possible to substantially reduce band shifts and transmissivityreductions. For example, a PbTe-based interference filter can, inaccordance with an embodiment of the present disclosure, have a bandshift of only about 0.03 nm/° C. or less. As an alternative to PbTe,PbSe or PbS, in some embodiments, the high refractive index layers maybe formed of Ge or the like.

In some embodiments of the present disclosure, a reference intensity isalso used in the determination of the amount of the species in thefluid. Thus a sensor arrangement may include the sensor of the firstaspect and a further similar sensor which may be used to obtain thisreference intensity. The further sensor can have the same features asthe first sensor except that its narrow bandpass filter transmitsmid-infrared radiation over a band of wavelengths corresponding to areference portion of the absorbance spectrum of the fluid. In such ascenario, the processor arrangement can be a shared processorarrangement of both sensors.

Another option, however, is to obtain the reference intensity using thefirst sensor. For example, the sensor may further include a secondnarrow bandpass filter transmitting mid-infrared radiation over a bandof wavelengths corresponding to a reference portion of the absorbancespectrum of the fluid, the or a further infrared detector detectingfiltered mid-infrared radiation transmitted through the second filter,and the processor arrangement measuring the reference intensity of thedetected mid-infrared radiation transmitted through the second filterand using the measured reference intensity in the determination of theamount of the species in the fluid. In some embodiments of the presentdisclosure, the first and second filters may be selectably positionablebetween a single detector and the window, or each of the first andsecond filters can have a respective detector. The second narrowbandpass filter may be configured such that its wavelength transmissionband is substantially temperature invariant over all temperatures in therange from about 25 to 150° C. Optional features of the first narrowbandpass filter may pertain also to the second narrow bandpass filter.

In some embodiments of the present disclosure, the sensor may be able tomeasure the amounts of more than one species in the fluid. For example,the sensor may include a plurality of the first narrow bandpass filters,each transmitting mid-infrared radiation over a band of wavelengthscorresponding to an absorbance peak of a respective species, the or arespective further infrared detector detecting the filtered mid-infraredradiation transmitted through each first filter, and the processorarrangement measuring the intensity of the detected mid-infraredradiation transmitted through each first filter and determiningtherefrom an amount of each species in the fluid. In some embodiments ofthe present disclosure, the first filters may be selectably positionablebetween a single detector and the window, or each first filter can havea respective detector.

In some embodiments of the present disclosure, when the sensor is ableto measure/monitor more than one species, the determined amounts of thespecies in the fluid may be in the form of a ratio of the concentrationsof the species.

In some embodiments of the present disclosure, the beam of mid-infraredlight/radiation may be pulsed. This may be achieved, for example, byproviding a mechanical chopper between the source and the window, or bypulsing the source.

In some embodiments of the present disclosure, the source may be a broadband thermal source or a narrower band source such as a light emittingdiode or a laser.

In some embodiments of the present disclosure, the detector may be athermopile, a pyroelectric or (particularly in subsea applications,where the low ambient temperatures can provide cooling) a photodiodedetector.

In some embodiments of the present disclosure, the window may be adiamond window or a sapphire window. In some embodiments of the presentdisclosure, the diamond window may be formed by chemical vapourdeposition. Sapphire has a cut off for mid-infrared radiation atwavelengths of about 5 to 6 microns, but sapphire windows can generallybe formed more cheaply than diamond windows. Thus, for absorption peaksbelow the cut-off (such as the CO₂ absorption peak at about 4.3microns), sapphire may be an alternative to diamond. In particular, fora given cost a larger window can be formed.

In some embodiments of the present disclosure, the sensor may furtherinclude a heater, which is operable to locally heat the window, therebycleaning the surface of the window in contact with the fluid. Merely byway of example, in some embodiments of the present disclosure, thewindow may comprise a conductive or semiconductive material (e.g. anarea of semiconductive boron-doped diamond or the like), and the heatermay comprise an electrical power supply that sends a current through thewindow to induce resistive heating thereof. For example, in someembodiments of the present disclosure, the diamond window may comprise acentral mid-infrared transmissive (e.g. undoped) area and an encirclingarea of semiconductive boron-doped diamond. The heater can induceresistive heating of the encircling area, and the central area can thenbe heated by conduction of heat from the encircling area. In someembodiments of the present disclosure, the heater may heat the window toa peak temperature of at least 400° C. In some embodiments of thepresent disclosure, the heater may maintain the peak temperature forless than one microsecond.

Alternatively or additionally, in some embodiments of the presentdisclosure, the sensor may further include an ultrasonic cleaner whichis operable to ultrasonically clean the surface of the window in contactwith the fluid. As another option, in some embodiments of the presentdisclosure, the sensor may be provided with a pressure pulsearrangement, which is operable to produce a pressure pulse in the fluidat the window, thereby cleaning the surface of the window in contactwith the fluid. In some embodiments of the present disclosure, thearrangement may produce a pressure pulse of at least 1000 psi (6.9 MPa)in the fluid.

In some embodiments of the present disclosure, the sensor may be locateddownhole.

In some embodiments of the present disclosure, the sensor may beadapted/used for monitoring a hydrocarbon species (typically aconstituent chemical group), which is a component of a hydrocarbonliquid. For example, the sensor may be used to determine amounts (e.g.concentrations) of CH₂ and/or CH₃ groups in the liquid. Additionally oralternatively, in some embodiments of the present disclosure, the sensormay determine a ratio of CH₂/CH₃ in the liquid. This ratio and a CH₂ orCH₃ group concentration can be used, for example, to detect whether adrilling fluid based on an unbranched synthetic oil has beencontaminated by crude oil.

In some embodiments of the present disclosure, the sensor may beadapted/used for monitoring a hydrate inhibitor species that isdissolved in a liquid. For example, the inhibitor may be a thermodynamicinhibitor such as methanol, ethanol, monoethylene glycol or diethyleneglycol, or it may be a kinetic inhibitor such as polyvinylpyrrolidone orpolyvinylcaprolactam. In development of an embodiment of the presentinvention, it was found that mid-infrared spectroscopy could be used todetect/monitor such inhibitors and, advantageously, the positions andheights of the mid-infrared absorbance peak(s) of such compounds tend tobe insensitive to salt content in the (typically water-based) liquid.Thus, in embodiments of the present disclosure, the sensitivity of thedetermination of the amount of the inhibitor to salt concentration canbe reduced. For monitoring a hydrate inhibitor, the sensor may, in someembodiments, be adapted for or used in subsea locations, such as subseapipelines.

In some embodiments of the present disclosure, the sensor may beadapted/used for monitoring a mineral acid species dissolved in aliquid. For example, the mineral acid may be HF, HCl, HBr or HI. HCl inparticular is extensively used for stimulation of carbonate formations.In some embodiments of the present disclosure, the sensor provides thatthe mineral acid concentration may be monitored to evaluate efficiencyof acidisation operations; where the high concentrations of mineralacids typically used in such operations often make pH measurementsunsuitable. In some embodiments of the present disclosure, thetransmission band of the first filter may be located on a dissociated Habsorbance peak of about 1050 cm⁻¹. In an embodiment of the presentdisclosure, the position and height of this peak tends to be insensitiveto salt content in the (typically water-based) liquid.

In some embodiments of the present disclosure, the sensor may beadapted/used for monitoring CO₂ concentration in the fluid. In general,attenuated total reflection mid-infrared sensing can only be used tosense condensed phases, but CO₂ is an exception, as it is stronglyabsorbing in the mid-infrared at a wavelength of about 4.3 μm. In someembodiments of the present disclosure, the sensor may have three firstnarrow bandpass filters corresponding to respective absorbance peaks ofwater, oil and CO₂. Such an arrangement can allow the CO₂ concentrationto be determined when the window is in contact with a liquid water-basedphase, a liquid oil-based phase, a mixture of liquid water and liquidoil-based phases, or a gas phase (i.e. when the window is dry). In someembodiments of the present disclosure, the sensor may also have thesecond narrow bandpass filter corresponding to a reference portion ofthe absorbance spectrum of the fluid. The transmission band of the firstfilters may be located at about 3330 cm⁻¹ (water), 2900 cm⁻¹ (oil) and2340 cm⁻¹ (CO₂). The transmission band of the second filter mayconveniently be located at about 2500 cm⁻¹.

From the above examples, it can be seen that, in some embodiments of thepresent disclosure, the monitored species may be:

-   -   a compound forming the fluid, or one or more compounds in a        mixture of compounds forming the fluid,    -   a constituent group (e.g. CH₂ or CH₃) of a compound forming the        fluid, or a constituent group common to one or more compounds in        a mixture of compounds forming the fluid,    -   one or more compounds or ions dissolved in a liquid, or    -   a constituent group of a compound or ion dissolved in a liquid,        or a constituent group common to one or more compounds or ions        dissolved in a liquid.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described by way of examplewith reference to the accompanying drawings in which:

FIG. 1A shows schematically a mid-infrared sensor, in accordance with anembodiment of the present disclosure;

FIG. 1B shows schematically the sensor of FIG. 1A implemented as amodule in a toolstring;

FIG. 2 shows schematically a narrow bandpass filter based on Fabry-Perotinterferometry, in accordance with an embodiment of the presentdisclosure;

FIG. 3 shows variation of dλ_(m)/λ_(m)dT for a suite of filtersfabricated with ZnSe as the low refractive index material and PbTe asthe high refractive index material, in accordance with an embodiment ofthe present disclosure;

FIG. 4A shows a plot of transmissivity against wavelength at a range oftemperatures from 25 to 200° C. for a PbTe-based filter having a passband centred at 4.26 μm, in accordance with embodiments of the presentdisclosure, and (b)

FIG. 4B shows a plot of transmissivity against wavelength at a range oftemperatures from 25 to 200° C. for a PbTe-based filter having a passband centred at 12.1 μm, in accordance with embodiments of the presentdisclosure;

FIG. 5A shows a reference intensity spectrum I₀ obtained from a fluidnot containing a given species;

FIG. 5B shows an intensity spectrum I obtained from the fluid containingthe species of FIG. 5A;

FIG. 5C shows the absorbance spectrum of the species of FIGS. 5A and 5B;

FIG. 6 shows intensity spectra obtained for dodecane dissolved indeuterated chloroform for increasing concentrations of dodecane, thespectra being superimposed with transmissivity plots for a first filterhaving a pass band of 3000 to 2800 cm⁻¹, and a second filter having apass band of 2000 to 1800 cm⁻¹;

FIG. 7 shows a plot of modified absorbance A′ against hydrocarboncontent for dodecane dissolved in deuterated chloroform;

FIG. 8 shows a plot of absorbance against dissolved CO₂ concentration inwater or hydrocarbon;

FIG. 9 shows absorbance spectra of the n-alkane series C₅ to C₁₇;

FIG. 10 shows plots of concentration of CH₂ groups and concentration ofCH₃ groups against carbon chain length for the n-alkane series C₅ toC₁₇;

FIG. 11 shows experimentally determined plots of absorbance againstconcentration of the respective group for n-alkane 2957 cm⁻¹ CH₃ peak,2853 cm⁻¹ CH₂ peak and 2922 cm⁻¹ CH₂ peak;

FIG. 12 shows mid-infrared absorbance spectra of a number of crude oils,with C₇ and C₁₀ alkane spectra also shown for reference;

FIG. 13 shows the mid-infrared absorbance spectra of the crude oils ofFIG. 12 superimposed with the spectra for three common base oils;

FIG. 14 shows again the mid-infrared absorbance spectra of the crudeoils of FIG. 12 superimposed with the spectra for two synthetic baseoils;

FIG. 15 shows a graph of CH₂/CH₃ ratio against CH₂ group concentrationwith crude oils plotted as squares and base oils as triangles, and alsoa curve for n-alkanes;

FIG. 16A shows mid-infrared absorbance spectra of monoethylene glycol inwater for different inhibitor concentrations from 0 to 100 vol %;

FIG. 16B shows mid-infrared absorbance spectra of methanol in water fordifferent inhibitor concentrations from 0 to 100 vol %;

FIG. 16C shows mid-infrared absorbance spectra of ethanol in water, fordifferent inhibitor concentrations from 0 to 100 vol %;

FIG. 17A shows a plot of absorbance against inhibitor concentrationfor-monoethylene glycol in water;

FIG. 17B shows a plot of absorbance against inhibitor concentration formethanol in water;

FIG. 17C shows a plot of absorbance against inhibitor concentration forethanol in water;

FIG. 18A shows mid-infrared absorbance spectra of 50 vol % monoethyleneglycol in water and in water saturated with NaCl;

FIG. 18B shows mid-infrared absorbance spectra of 50 vol % methanol inwater and in water saturated with NaCl;

FIG. 18C shows mid-infrared absorbance spectra of 50 vol % ethanol inwater and in water saturated with NaCl;

FIG. 19 shows mid-infrared absorbance spectra at 50 vol % water ofmixtures of monoethylene glycol and methanol, with the mixtures varyingfrom 100% monoethylene glycol to 100% methanol;

FIG. 20 shows plots of absorbance against concentration for respectivelymonoethylene glycol (diamonds) based on the leftmost peak of FIG. 19 andmethanol (squares) based on the rightmost peak of FIG. 19;

FIG. 21 shows mid-infrared absorbance spectra of polyvinylpyrrolidone inwater, for different inhibitor concentrations from 0 to 5 wt %;

FIG. 22 shows a plot of absorbance against inhibitor concentration forpolyvinylpyrrolidone in water;

FIG. 23 shows mid-infrared absorbance spectra of 5 wt %polyvinylpyrrolidone in water and in water saturated with NaCl

FIG. 24 shows mid-infrared absorbance spectra of HCl in water, fordifferent HCl concentrations from 0 to 40 wt %;

FIG. 25 shows a plot of absorbance against HCl concentration for HCl inwater;

FIG. 26 shows mid-infrared absorbance spectra of DCl in D₂O, fordifferent DCl concentrations from 0 to 35 wt %;

FIG. 27 shows a plot of absorbance against DCl concentration for DCl inD₂O;

FIG. 28 shows mid-infrared absorbance spectra of 4.2 M HCl in water, 4.7M HBr in water and 4.5 M HI in water;

FIG. 29 shows the plots of absorbance against acid concentration forHCl, HBr and HI in water;

FIG. 30A shows a mid-infrared absorbance spectrum for a water phase andCO₂;

FIG. 30B corresponds to FIG. 30A and shows a plot of absorbance againstCO₂ concentration for CO₂ in H₂O;

FIG. 31A shows a mid-infrared absorbance spectrum for an oil phase andCO₂;

FIG. 31B corresponds to FIG. 31A and shows a plot of absorbance againstCO₂ concentration for CO₂ in oil;

FIG. 32A shows a mid-infrared absorbance spectrum for a water phase, anoil phase and CO₂; and

FIG. 32B shows a plot of absorbance against CO₂ concentration for CO₂ ingas phase.

In the appended figures, similar components and/or features may have thesame reference label. Further, various components of the same type maybe distinguished by following the reference label by a dash and a secondlabel that distinguishes among the similar components. If only the firstreference label is used in the specification, the description isapplicable to any one of the similar components having the same firstreference label irrespective of the second reference label.

DETAILED DESCRIPTION

The ensuing description provides preferred exemplary embodiment(s) only,and is not intended to limit the scope, applicability or configurationof the invention. Rather, the ensuing description of the preferredexemplary embodiment(s) will provide those skilled in the art with anenabling description for implementing a preferred exemplary embodimentof the invention, it being understood that various changes may be madein the function and arrangement of elements without departing from thescope of the invention.

Specific details are given in the following description to provide athorough understanding of the embodiments. However, it will beunderstood by one of ordinary skill in the art that embodiments maybepracticed without these specific details. For example, well-knowncircuits, processes, algorithms, structures, and techniques may be shownwithout unnecessary detail in order to avoid obscuring the embodiments.

Also, it is noted that the embodiments may be described as a processwhich is depicted as a flowchart, a flow diagram, a data flow diagram, astructure diagram, or a block diagram. Although a flowchart may describethe operations as a sequential process, many of the operations can beperformed in parallel or concurrently. In addition, the order of theoperations may be re-arranged. A process is terminated when itsoperations are completed, but could have additional steps not includedin the figure. A process may correspond to a method, a function, aprocedure, a subroutine, a subprogram, etc. When a process correspondsto a function, its termination corresponds to a return of the functionto the calling function or the main function.

Moreover, as disclosed herein, the term “storage medium” may representone or more devices for storing data, including read only memory (ROM),random access memory (RAM), magnetic RAM, core memory, magnetic diskstorage mediums, optical storage mediums, flash memory devices and/orother machine readable mediums for storing information. The term“computer-readable medium” includes, but is not limited to portable orfixed storage devices, optical storage devices, wireless channels andvarious other mediums capable of storing, containing or carryinginstruction(s) and/or data.

Furthermore, embodiments may be implemented by hardware, software,firmware, middleware, microcode, hardware description languages, or anycombination thereof. When implemented in software, firmware, middlewareor microcode, the program code or code segments to perform the necessarytasks may be stored in a machine readable medium such as storage medium.A processor(s) may perform the necessary tasks. A code segment mayrepresent a procedure, a function, a subprogram, a program, a routine, asubroutine, a module, a software package, a class, or any combination ofinstructions, data structures, or program statements. A code segment maybe coupled to another code segment or a hardware circuit by passingand/or receiving information, data, arguments, parameters, or memorycontents. Information, arguments, parameters, data, etc. may be passed,forwarded, or transmitted via any suitable means including memorysharing, message passing, token passing, network transmission, etc.

It is to be understood that the following disclosure provides manydifferent embodiments, or examples, for implementing different featuresof various embodiments. Specific examples of components and arrangementsare described below to simplify the present disclosure. These are, ofcourse, merely examples and are not intended to be limiting. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.Moreover, the formation of a first feature over or on a second featurein the description that follows may include embodiments in which thefirst and second features are formed in direct contact, and may alsoinclude embodiments in which additional features may be formedinterposing the first and second features, such that the first andsecond features may not be in direct contact.

FIG. 1A shows schematically a mid-infrared sensor, in accordance with anembodiment of the present disclosure, comprising a thermal broad bandmid-infrared source 1, a mechanical chopper 2 that pulses a beam 3 ofmid-infrared radiation which issues from the source, a diamond window 4,a set of selectively movable first narrow bandpass filters 5 and asecond narrow bandpass filter 5′, respective mid-infrared detectors 6for the filters, and a processor arrangement 7. The sensor may beencased in a protective housing which allows the sensor to be deployeddownhole, the window 4 being positioned for contact with the fluid to bemonitored. In some embodiments of the present disclosure, mid-infraredwaveguides (not shown) may optically connect the source, window and thedetectors. Suitable waveguides can be formed from optical fibres (e.g.hollow fibres or chalcogenide fibres), solid light pipes (e.g. sapphirepipes), or hollow light pipes (e.g. air or vacuum filled) with areflective (e.g. gold) coating.

As the output from detector 6 changes with temperature, even smallchanges in temperature may cause a large drift in signal output.However, in some embodiments of the present disclosure, pulsing the beam3 allows the output signal of the detector to be frequency modulated,enabling removal of the environmental temperature effects from thesignal. More particularly, the environment effects can be largelyremoved electronically by a high pass filter, because the time constantfor environment effects tends to be much longer than the signalfrequency. In some embodiments of the present disclosure, the detectoroutput is AC-coupled to an amplifier. The desired signal can then beextracted e.g. electronically by lock-in amplification orcomputationally by Fourier transformation.

Instead of the thermal source 1 and the mechanical chopper 2, in someembodiments of the present disclosure, the pulsed beam 3 may be producedby a pulsable thermal source, light emitting diode or laser sourceand/or the like. Pulsing the source in this way can give the samebenefit of frequency modulation measurement, plus it may reduceresistive heating effects.

The beam 3 enters at one edge of the window 4, and undergoes a number oftotal internal reflections before emerging from the opposite edge. Thetotal internal reflection of the infrared radiation at the fluid side ofthe window is accompanied by the propagation of an evanescent wave intothe fluid. As the fluid preferentially absorbs certain wavelengths,depending on its chemical composition, this causes the emerging beam tohave a characteristic variation in intensity with wavelength.

In some embodiments of the present disclosure, the window 4 may bemechanically able to withstand the high pressures and temperaturestypically encountered downhole. In some embodiments of the presentdisclosure, the window may be chemically stable to fluids encountereddownhole and transparent in the mid-IR wavelength region. In someembodiments of the present disclosure, the window may comprise diamond,sapphire and/or the like.

The first narrow bandpass filters 5 each transmit mid-infrared radiationover a band of wavelengths corresponding to an absorbance peak of arespective species in the fluid, while the second narrow bandpass filter5′ transmits mid-infrared radiation over a band of wavelengthscorresponding to a reference portion of the absorbance spectrum of thefluid. The beam 3 then passes through a selected one of the narrowbandpass filters and is detected at the respective detector 6. Insteadof having a plurality of detectors, each movable with its correspondingfilter (as indicated by the double-headed arrow), a further option is tohave a single detector in front of which the filters are selectivelymovable.

The detector 6 may comprise semiconductor photo-diodes (particularly insubsea applications), thermopiles or pyroelectric detectors.

an embodiment of the present disclosure the processor arrangement 7receives a signal from the respective detector 6, which it processes tomeasure the intensity of the detected mid-infrared radiation transmittedthrough each filter 5, 5′, and may either detect the respective speciesin the fluid or determine from the measured intensity, as discussed inmore detail below, an amount of the respective species in the fluid.

Also discussed in more detail below, the sensor comprise have a heater 8which is operable to locally heat the window 4, thereby cleaning thesurface of the window in contact with the fluid. Other options, however,are to clean the window ultrasonically (as described for example in U.S.Pat. No. 7,804,598 incorporated by reference herein for all purposes),or with a mechanical wiper.

FIG. 1B shows schematically how the sensor, in accordance withembodiments of the present disclosure may be implemented as a module ina toolstring. In an embodiment of the present disclosure, the source 1and chopper 2 may be contained in a source unit 9 and filters 5, 5′ anddetectors 6 may be contained in a detector unit 10. These are locatedclose to the window 4 that is in contact with a tool flowline 11. Insome embodiments of the present disclosure, the sensor is packaged in aprotective metal chassis 12 to withstand the high pressure of the fluidin the flowline. In some embodiments of the present disclosure, thewindow is sealed into the chassis also to withstand the high pressures,and its packaging ensures no direct source light strays into thedetectors.

Narrow Bandpass Filters

In some embodiments of the present disclosure, the narrow bandpassfilters 5, 5′ may be based on Fabry-Perot interferometry. As shown inFIG. 2, in some embodiments of the present disclosure, each filter maycomprise a substrate S of low refractive index and thickness d. Onopposing surfaces of the substrate are stacked alternatinghigh-reflectivity dielectric layers of high H and low L refractive indexdeposited onto the substrate using techniques such as ion-beamsputtering or radical-assisted sputtering. Each layer in the stacks ofalternating layers of high H and low L refractive index has an opticalthickness of a quarter wavelength.

In an embodiment of the present disclosure, the optical thickness ndcosθof the substrate S, where n is the refractive index of the substrate, isequal to an integer number of half wavelengths λ_(m), where λ_(m) is thepeak transmission wavelength, corresponding approximately to the centrewavelength of the pass band of the filter. The condition for thetransmission of radiation of wavelength λ_(m) through the filter is thusmλ_(m)/2=ndcosθ, where m is an integer.

The spectral region of conventional narrow bandpass dielectric filtersdesigned to operate in the mid-infrared spectral regions shiftssystematically to longer wavelengths with increasing temperature. Theorigin of the change in λ_(m) with temperature is a change in thematerial properties with temperature of the dielectric materials thatcomprise the layers of the filter.

However, in accordance with embodiments of the present disclosure, anapproach for the configuration and fabrication of mid-infrared narrowbandpass filters is provided where the filters have substantiallytemperature invariant optical properties over a wide temperature range.

In accordance with embodiments of the present disclosure, the approachcan be considered by the design of the filter:

(LH)^(x1)(LL)^(y1)(HL)^(x2)(LL)^(y2) . . . (LL)^(yN)(HL)^(xN+1)

consisting of a total of y half wavelength spacers (cavities) LL of lowrefractive index material in N cycles (y=Σ_(i), LH being the stacks ofx_(i) quarter wavelength layers of alternating of high and lowrefractive index material in the N cycles. The reflections wavelength ofthe quarter wavelength reflector stack (which is the only reflection toundergo constructive interference), irrespective of the values of x_(i)and N, can be expressed as:

λ_(m)=2(n _(L) d _(L) +n _(H) d _(H))

for first order reflections (m=0). The temperature variation of thewavelength in the reflector stack dλ_(m)/dT|_(s) can be expressed as:

${\frac{d\; \lambda_{m}}{dT}\text{|}_{s}} = {{2n_{L}{d_{L}( {C_{L} + \frac{{dn}_{L}}{n_{L}{dT}}} )}} + {2n_{H}{d_{H}( {C_{H} + \frac{{dn}_{H}}{n_{H}{dT}}} )}}}$

where C_(L) and C_(H) are the coefficients of linear expansion of thelow and high refractive index materials, respectively. From eqn. [1] forfirst order reflection and normal incidence (i.e., m=1 and θ=0°), thecorresponding temperature dependence dλ_(m)/dT|_(c) of the cavity layerof low refractive index material is given by:

${\frac{d\; \lambda_{m}}{dT}\text{|}_{c}} = {2{yn}_{L}{d_{L}( {C_{L} + \frac{{dn}_{L}}{n_{L}{dT}}} )}}$

noting that y is the total number of half wavelength cavity layers. Thetotal change in wavelength with temperature dλ_(m)/dT|_(T) is given bythe sum of dλ_(m)/dT|_(c) and dλ_(m)/dT|_(s);

${\frac{d\; \lambda_{m}}{dT}\text{|}_{T}} = {{2( {1 + y} )n_{L}{d_{L}( {C_{L} + \frac{{dn}_{L}}{n_{L}{dT}}} )}} + {2n_{H}{d_{H}( {C_{H} + \frac{{dn}_{H}}{n_{H}{dT}}} )}\mspace{14mu} {or}}}$${\frac{d\; \lambda_{m}}{\lambda_{m}{dT}}\text{|}_{T}} = {{( {1 + y} )( {C_{L} + \frac{{dn}_{L}}{n_{L}{dT}}} )} + ( {C_{H} + \frac{{dn}_{H}}{n_{H}{dT}}} )}$

noting that n_(L)d_(L)=n_(H)d_(H) at the temperature for which thefilter is designed for use. Clearly dλ_(m)/dT|_(T) can only be zero ifthe value of dn/dT for one of the materials is negative. This conditioncan be fulfilled by high refractive index materials such as PbTe, PbSeor PbS. For close matching of the value of dλ_(m)/dT|_(T) to zero, thewavelength dependence of ni temperature and wavelength dependence ofdn_(i)/dT can be taken into account.

The condition dλ_(m)/dT|_(T)=0 is given approximately by:

$\frac{{dn}_{H}}{n_{H}{dT}} = {{- ( {1 + y} )}\frac{{dn}_{L}}{n_{L}{dT}}}$

noting that C_(i) is considerably smaller than dn_(i)/n_(i)dT for mostmaterials used in mid-infrared filters. The term (1+y) can be chosen tosatisfy the above expression depending on the choice of low refractiveindex material. For example, with ZnSe and PbTe for the low and highrefractive index materials, respectively, and using the material valuesof bulk phases n_(L)=2.43, n_(H)=6.10, dn_(L)/dT=6.3×10⁻⁵ K⁻¹ anddn_(H)/dT=−2.1×10⁻³ K⁻¹ for λ_(m)=3.4 μm, the expression is satisfiedwith y=13.3, i.e., approximately 13 half wavelength cavity layers arerequired to achieve the condition dλ_(m)/dT|_(T)=0.

There is considerable variation in the values of the material properties(n_(H), dn_(H)/dT, C_(H), etc.) that appear in for thin films in amultilayer structure and therefore in the predicted value ofdλ_(m)/dT_(T) or the value of y required to achieve the conditiondλ_(m)/λ_(m)dT=0. The uncertainty is particularly severe for the valueof dn_(H)/dT for PbTe in view of its magnitude and influence on thevalue of y. For example, the value of dn/dT for PbTe at λ_(m)=5 μm hasbeen reported to be −1.5×10⁻³ K⁻¹ by Zemel, J. N., Jensen, J. D. andSchoolar, R. B., “ELECTRICAL AND OPTICAL PROPERTIES OF EPITAXIAL FILMSOF PBS, PBSE, PBTE AND SNTE ”, Phys. Rev. 140, A330-A343 (1965),−2.7×10⁻³ K⁻¹ by Piccioli, N., Besson, J. M. and Balkanski, M., “OPTICALCONSTANTS AND BAND GAP OF PBTE FROM THIN FILM STUDIES BETWEEN 25 AND300° K.”,J. Phys. Chem. Solids, 35, 971-977 (1974), and −2.8×10⁻³ K⁻¹ byWeiting, F. and Yixun, Y., “TEMPERATURE EFFECTS ON THE REFRACTIVE INDEXOF LEAD TELLURIDE AND ZINC SELENIDE ”, Infrared Phys., 30, 371-373(1990). From the above expression, the corresponding values of y (to thenearest integer) are 9, 17 and 18, respectively.

In view of the uncertainties in the value of dn/dT for PbTe andtherefore the number of low refractive index half wavelength spacersrequired to achieve dλ_(m)/dT=0, a more useful approach is to determinethe experimental value of dλ_(m)/dT as a function of the opticalthickness of the low refractive index cavities for a suite of filtersfabricated by the same method.

FIG. 3 shows the variation of dλ_(m)/λ_(m)dT for a suite of filtersfabricated with ZnSe as the low refractive index material and PbTe asthe high refractive index material. The plot shows that a particularvalue of dλ_(m)/λ_(m)dT can be achieved by controlling the ratio of lowto high refractive index materials in the filter (i.e., a parametersimilar to y in the above expression). FIG. 3 shows that for λ_(m)<5 μm,the condition dλ_(m)/λ_(m)dT=0 is met by a 4:4:4 (i.e., 3 fullwavelength or 6 half wavelength cavities (y=6)) filter, while forλ_(m)>5 μm a 6:4:6 (y=8) filter is required.

The approach illustrated by FIG. 3 can be used, in accordance with anembodiment of the present disclosure, to fabricate substantiallytemperature invariant filters over the entire mid-infrared spectralrange. In some embodiments of the present disclosure, the substrate maybe formed of Si, SiO₂, Al₂O₃, Ge or ZnSe. In some embodiments of thepresent disclosure, high refractive index layers can be formed of PbTe,PbSe or PbS, although Ge is also an option. In some embodiments of thepresent disclosure, the low refractive index layers can be formed of ZnSor ZnSe.

FIGS. 4A and 4B show plots of transmissivity against wavelength at arange of temperatures from 25 to 200° C. FIG. 4A shows a plot for aPbTe-based filter having a pass band centred at 4.26 μm with optimumoptical matching to the substrate and 3 full wavelength thicknesscavities (4:4:4), and FIG. 4B shows a plot for a degenerate PbTe-basedfilter having a pass band centred at 12.1 μm with 3 half wavelengthcavities (2:2:2). Similar filters can be produced having pass bandscentred at other mid-infrared wavelengths. The value of dλ_(m)/dT forthe λ_(m)=4.26 μm (4:4:4) filter varies from −0.04 nm/K at 20° C. to+0.03 nm/K at 200° C. and is essentially zero over the temperature range80-160° C. The value of dλ_(m)/dT for the λ_(m)=12.1 μm (2:2:2) filteris −0.21 nm/K, over the temperature range 20-200° C. This allows suchfilters to deployed downhole, where temperatures can vary from about 25to 200° C., without the pass band of the filter shifting to such anextent that it no longer corresponds to the absorbance peak of itsrespective species.

Spectroscopy

The Beer-Lambert law applied to the sensor of FIGS. 1A and 1B providesthat:

A=−log₁₀(I/I ₀)

where A is the absorbance spectrum by a species in the fluid having anabsorbance peak at a wavelengths corresponding to the pass band of thefilter 5, I is the intensity spectrum of the infrared radiation detectedby the detector 6, and Io is a reference intensity spectrum. Forexample, FIGS. 5A to 5C show (a) a reference intensity spectrum Ioobtained from a fluid not containing a given species, (b) an intensityspectrum I obtained from the fluid containing the species, and (c) theabsorbance spectrum of the species.

FIG. 6 shows intensity spectra obtained for dodecane dissolved indeuterated chloroform for increasing concentrations of dodecane. Withincreasing hydrocarbon content there is increased absorption in a firstwavenumber range of 3000 to 2800 cm⁻¹. Conversely, the increasinghydrocarbon content has substantially no effect on absorption in asecond wavenumber range of 2000 to 1800 cm⁻¹. The second range can thusbe used as the reference to the first range. Superimposed on FIG. 6 aretransmissivity plots for a first filter having a pass band of 3000 to2800 cm⁻¹, and a second filter having a pass band of 2000 to 1800 cm⁻¹.Two spectra are thus, in effect, detected by the filters, the firstspectrum being the unfiltered spectrum multiplied by the transmissivityof the first filter and the second sub-spectrum being the unfilteredspectrum multiplied by the transmissivity of the second filter. The passband areas of the spectra (as determined by the strengths of the signalsreceived by the photodiode detectors), correspond to respectiveintensity measurements BA and BA₀. These are thus used to calculate amodified absorbance A′ for dodecane dissolved in deuterated chloroformwhich is ln(BA/BA₀.

FIG. 7 shows a plot of modified absorbance A′ against hydrocarboncontent for dodecane dissolved in deuterated chloroform. The plotexhibits an approximately linear relationship between A′ and hydrocarboncontent.

Other species can be monitored in this way. For example, FIG. 8 shows aplot of absorbance against dissolved CO₂ concentration in water orhydrocarbon under the high partial pressures and temperatures typical ofoil field wellbore conditions.

Hydrocarbon Characterisation

A mid-infrared sensor in accordance with an embodiment of the presentdisclosure may be used to characterise hydrocarbons downhole. Theability of the sensor to operate under a full range of downholetemperatures, among other things, is particularly advantageous. Thesensor may be deployed, for example, in a drilling, production well orwireline sampling tool.

FIG. 9 shows absorbance spectra of the n-alkane series C₅ to C₁₇. Themid-infrared spectrum is largely determined by CH₂ and CH₃ groups. FIG.10 shows plots of concentration of CH₂ groups and concentration of CH₃groups against carbon chain length. With increasing chain length, therelative number of CH₂ to CH₃ groups increases. This is reflected inFIG. 9 by the CH₂ peaks increasing in height and the CH₃ peaksdecreasing in height as the chain length increases.

FIG. 11 shows experimentally determined plots of absorbance againstconcentration of the respective group for the 2957 cm⁻¹ CH₃ peak, the2853 cm⁻¹ CH₂ peak and the 2922 cm⁻¹ CH₂ peak. The plots demonstrate forall peaks reasonable linearity between absorbance and concentration(e.g. A(2957 cm⁻¹)=0.0068[CH₃]+0.030 and e.g. A(2853cm⁻¹)=0.0065[CH₂]−0.127), and also reasonable sensitivity of absorbanceto change in concentration.

Thus one option, in accordance with an embodiment of the presentdisclosure, is to perform quantitative analysis of CH₂ or CH₃ groupconcentration based on infrared intensity measurements (a) filtered overa band corresponding to a respective peak of the dissolved species and(b) filtered over a band corresponding to a reference portion of theabsorbance spectrum.

Another option, in accordance with an embodiment of the presentdisclosure, is to use filters having pass bands at, for example, 2957cm⁻¹ (for CH₃) and 2841 cm⁻¹ (for CH₂) to enable the CH₂/CH₃ ratio to bedetermined. This can useful for detecting contamination of oil-baseddrill fluids by crude oil during sampling.

In particular, crude oils show only modest variation in CH₂/CH₃ ratio.

FIG. 12 shows mid-infrared absorbance spectra of a number of crude oils,with C₇ and C₁₀ alkane spectra also shown for reference. For North Seacrude the CH₂/CH₃ ratio is 3.48, for

Cold Lake heavy oil is 3.65 and for Marmul crude it is 4.22. The CH₂/CH₃ratios are thus within the range of n-alkanes C₈-C₁₁. FIG. 13 shows themid-infrared absorbance spectra of the same crude oils superimposed withthe spectra for three common base oils (HT 40N a, Escaid 110 andClairsol 370). There is little discrimination between the spectra of thecrude oils and the base oils. However, use of a synthetic base oilconsisting of straight-chain alkanes enhances the contrast in theCH₂/CH₃ ratio. For example, Biobase 300 base oil available from M-I hasa CH₂/CH₃ ratio of 4.13 and Sipdrill 2/0 base oil also from M-I has aCH₂/CH₃ ratio of 4.84.

FIG. 14 shows again the mid-infrared absorbance spectra of the crudeoils but now superimposed with the spectra for these two synthetic baseoils.

Thus, using a reference filter and respective filters for CH₂ and forCH₃, in accordance with an embodiment of the present disclosure, allowsan oil to be plotted on a graph of CH₂/CH₃ ratio against CH₂ groupconcentration.

FIG. 15 shows such a graph, with crude oils plotted as squares and baseoils as triangles, and for reference the curve for n-alkanes alsoprovided. Broadening of spectra for crude oils over base oils is one ofthe reasons why crude oils tend to exhibit higher a CH₂/CH₃ ratio for agiven CH₂ group concentration than base oils. Nonetheless, the twotriangles at far right are the Biobase 300 and Sipdrill 2/0 syntheticbase oils, demonstrating that such a plot provides a basis fordiscriminating between synthetic non-branched base oils and crude oilsand thus detecting base oil contamination by crude oil.

Hydrate Inhibitor Concentration

A further possible use for a sensor in accordance with an embodiment ofthe present disclosure is to monitor hydrate inhibitor concentrations,for example in subsea locations, such as subsea pipelines.

In the hydro-carbon industry, gas hydrates can form, particularly, inproduction pipelines. This is undesirable as the hydrates canagglomerate and block the flow and/or cause equipment damage. Twosolutions are generally proposed. One is to add thermodynamicinhibitors, such as methanol, ethanol, monoethylene glycol or diethyleneglycol, to the flow. These compounds may be recovered and recirculated.Although such thermodynamic inhibitors are cheap, they usually have tobe added in large quantities in order to have a thermodynamic effect oflowering the hydrate formation temperature and/or delaying hydrateformation. The second is to add kinetic inhibitors, such aspolyvinylpyrrolidone or polyvinylcaprolactam, to the flow. These work byslowing down the rate of hydrate nucleation and/or reducing hydrateagglomeration. They can be effective in lower doses, but are moreexpensive than most thermodynamic inhibitors.

With both types of inhibitor it is important to be able to measure theconcentration of inhibitor in the liquid. Salt can be present in theliquid, sometimes in varying amounts, and may make such measurementsproblematic. However, the positions of mid-infrared absorption peaks ofmany inhibitors are not sensitive to salt concentration, making amid-infrared sensor in accordance with an embodiment of the presentdisclosure an attractive proposition for measuring inhibitorconcentration.

FIGS. 16A to 16C show mid-infrared absorbance spectra of (a)monoethylene glycol in water, (b) methanol in water, and (c) ethanol inwater, for different inhibitor concentrations from 0 to 100 vol %.

FIGS. 17A to 17C show plots of absorbance against inhibitorconcentration for (a) monoethylene glycol in water, (b) methanol inwater, and (c) ethanol in water. For FIG. 17A, the absorbances weremeasured using a band located on the 1084 cm⁻¹ absorbance peak and aband corresponding to a reference portion of the absorbance spectrum.For FIG. 17B, the absorbances were measured using a band located on the1020 cm⁻¹ absorbance peak and a band corresponding to a referenceportion of the absorbance spectrum. For FIG. 17C, the absorbances weremeasured using a band located on the 1045 cm⁻¹ absorbance peak and aband corresponding to a reference portion of the absorbance spectrum.The plots of FIGS. 17A to 17C demonstrate good linearity betweenabsorbance and concentration.

FIGS. 18A to 18C show mid-infrared absorbance spectra of (a) 50 vol %monoethylene glycol in water and in water saturated with NaCl, (b) 50vol % methanol in water and in water saturated with NaCl, and (c) 50 vol% ethanol in water and in water saturated with NaCl. For monoethyleneglycol, the 1084 cm⁻¹ absorbance peak shifts in the presence of NaCl,but the position of an alternative 1040 cm⁻¹ absorbance peak is static.This illustrates how a mid-infrared sensor in accordance with thepresent disclosure may be used to measure species, such as monoethyleneglycol in the presence of NaCl. In particular, the mid-infrared sensorcan be tuned, i.e., the filter can be tuned, to account for absorbancepeak shifts in the presence of NaCl. For methanol, the position of the1020 cm⁻¹ absorbance peak is static, and for ethanol the position of the1044 cm⁻¹ absorbance peak is static.

FIG. 19 shows mid-infrared absorbance spectra at 50 vol % water ofmixtures of monoethylene glycol and methanol, with the mixtures varyingfrom 100% monoethylene glycol to 100% methanol. The right hand peakgrows with increasing methanol, and the two left hand peaks grow withincreasing monoethylene glycol. FIG. 20 shows plots of absorbanceagainst concentration for respectively monoethylene glycol (diamonds)based on the leftmost peak and methanol (squares) based on the rightmostpeak. Relative amounts of monoethylene glycol and methanol in a mixturecan be determined from such plots.

FIG. 21 shows mid-infrared absorbance spectra of polyvinylpyrrolidone inwater, for different inhibitor concentrations from 0 to 5 wt %, and FIG.22 shows a plot of absorbance against inhibitor concentration forpolyvinylpyrrolidone in water, using a band located on the 1295 cm⁻¹absorbance peak and a band corresponding to a reference portion of theabsorbance spectrum. The plot of FIG. 22 demonstrates good linearitybetween absorbance and concentration. FIG. 23 shows mid-infraredabsorbance spectra of 5 wt % polyvinylpyrrolidone in water and in watersaturated with NaCl, the position of the 1295 cm⁻¹ absorbance peak beingstatic. Thus as with the other species, such an inhibitor can bemeasured in the presence of salt as absorption can be differentiatedand/or the sensor can be tuned for movement of the peaks in the presenceof salt.

Mineral Acid Concentration

Another possible use for a sensor in accordance with an embodiment ofthe present disclosure is to monitor mineral acid concentrations.Mineral acid measurement/monitoring is problematic in general because ofthe nature of the acids and the effect the acids have on sensor systems.However, the inventors have found that, surprisingly, acid concentrationmay be determined from mid-infrared spectroscopy.

Mineral acids may be in many industries, including the petroleumindustry. For example, HCl is extensively pumped downhole forstimulation of carbonate formations. The high mineral acid concentrationtypically used in such operations often makes pH measurementsunsuitable. However, the sensor in accordance with an embodiment of thepresent disclosure may be deployed to enable HCl concentration to bemonitored to evaluate acidisation efficiency. The ability of the sensorin accordance with the first aspect of the present disclosure to operateunder a full range of downhole temperatures may also be advantageous.

FIG. 24 shows mid-infrared absorbance spectra of HCl in water, fordifferent HCl concentrations from 0 to 40 wt %, and FIG. 25 shows a plotof absorbance against HCl concentration for HCl in water, using a bandlocated on the 1050cm⁻¹ absorbance peak and a band corresponding to areference portion of the absorbance spectrum. The plot of FIG. 25demonstrates good linearity between absorbance and concentration. NaClis not a factor with respect to HCl use in the petrochemical industry,however, CaCl will be a return product in downhole HCl applications.

The 1050 cm⁻¹ absorbance peak is apparently due to dissociated HCl, thepeak only emerging as the HCl concentration rises. Further evidence thatthe peak is due to dissociated HCl comes from measurements of DCl inD20. FIG. 26 shows mid-infrared absorbance spectra of DCl in D₂O, fordifferent DCl concentrations from 0 to 35 wt %. As expected, all thepeaks shown in FIG. 24 are shifted in FIG. 26 to lower wavenumbers byapproximately 1/√2. For completeness, FIG. 27 shows a plot of absorbanceagainst DCl concentration for DCl in D₂O, using a band located on the850 cm⁻¹ absorbance peak (shifted from 1050 cm⁻¹ in FIG. 24) and a bandcorresponding to a reference portion of the absorbance spectrum.

The 1050 cm⁻¹ absorbance peak is also exhibited by HBr and HI, asillustrated by FIG. 28 which shows mid-infrared absorbance spectra of4.2 M HCl in water, 4.7 M HBr in water and 4.5 M HI in water, suggestingthat the peak is caused by a hydrated proton. FIG. 29 shows thecorresponding plots of absorbance against acid concentration using aband located on the 1050 cm⁻¹ absorbance peak.

Carbon Dioxide Concentration

Another possible use for a sensor in accordance with an embodiment ofthe present disclosure is to monitor CO₂ concentrations. The analysis offluid samples from hydrocarbon wells for the determination of phasebehaviour and chemical composition is a critical step in the evaluationof the producibility and economic value of the hydrocarbon reserves. Animportant factor in determining the economic value of gas and liquidhydrocarbon reserves is their chemical composition, particularly theconcentration of gaseous components, such as carbon dioxide. Similarly,the monitoring of fluid composition during production operations canhave an important bearing on reservoir management decisions, such asceasing production from certain zones or applying chemical treatments toproducing wells.

A mid-infrared sensor, in accordance with an embodiment of the presentdisclosure comprising a temperature invariant filter, may be used tomonitor CO₂ concentrations downhole. In particular, in accordance withembodiments of the present disclosure, the sensor may comprise threenarrow bandpass filters 5 corresponding to respective absorbance peaksof water, oil and CO_(2,) and a second narrow bandpass filter 5′ for areference portion of the absorbance spectrum. Such an arrangement allowsthe CO₂ concentration to be determined when the window 4 is wetted by aliquid water phase, a liquid oil phase, a mixture of liquid water andliquid oil phases, or when the window is dry.

For example, FIG. 30A shows an absorbance spectrum for the case wherethe window 4 is wetted by a water phase. The spectrum is characterisedby high absorption by water at 3.00 μm, almost no absorption by oil at3.45 μm. The CO₂ concentration is proportional to the net CO₂absorption, which is the difference between the CO₂ channel at 4.27 μmand the reference channel at 4.00 μm. The proportionality constantallowing CO₂ concentration in the water phase to be determined from CO₂absorption can be obtained from an experimental plot of CO₂ absorbanceagainst dissolved CO₂ concentration in water, such as shown in FIG. 30B.

Similarly, FIG. 31A shows an absorbance spectrum for the case where thewindow 4 is wetted by an oil phase. The spectrum is characterised byhigh absorption by oil at 3.45 um μm almost no absorption by water at3.00 μm. Again, the CO₂ concentration is proportional to the net CO₂absorption, which is the difference between the CO₂ channel at 4.27 μmand the reference channel at 4.00 μm. The proportionality constantallowing CO₂ concentration in the oil phase to be determined from CO₂absorption can be obtained from an experimental plot of CO₂ absorbanceagainst dissolved CO₂ concentration in oil, such as shown in FIG. 31B.

Next, FIG. 32A shows an absorbance spectrum for the case where thewindow 4 is wetted by a mixture of water and oil phases. The spectrum ischaracterised by absorption by water at 3.00 μm and by oil at 3.45 μm.Again the CO₂ concentration is proportional to the net CO₂ absorption,which is the difference between the CO₂ channel at 4.27 μm and thereference channel at 4.00 μm. However, the proportionality constant isslightly different for water and for oil because their refractiveindices, and thus their depths of investigation, are different.

Specifically, oil has higher refractive index than water, thus its depthof investigation is deeper and potentially more CO₂ is sensed by thesensor in oil than in water. Thus, when the window is wetted by amixture of both water and oil phase, the mixture proportionalityconstant is between those of water and oil, but can be calculated. Forexample, a simple approach is to use a “lever rule”, whereby if thewater peak height is X % of its full height and the oil peak height is(100−X)% of its full height, the mixture proportionality constant is thesum of X % of the water proportionality constant and (100−X)% of the oilproportionality constant. More elaborate schemes can be used, but thesimple “lever rule” approach works reasonably well because thedifference between the water and oil proportionality constants is in anyevent not great.

Under some circumstances, the sensor window 5 may be dry. The spectrumis characterised by almost no absorption by water at 3.00 μm or by oilat 3.45 μm. CO₂ concentration is proportional to the net CO₂ absorption,which is the difference between the CO₂ channel at 4.27 μm and thereference channel at 4.00 μm. The proportionality constant allowing CO₂concentration in the gas phase to be determined from CO₂ absorption canbe obtained from an experimental plot of CO₂ absorbance against CO₂concentration in gas phase, such as shown in FIG. 32B.

Monitoring of CO₂ concentration can be particularly useful whenperformed in combination with monitoring of mineral acid concentrations.In particular, the mineral acid sensor can provide a measure of how muchacid is being deployed to stimulate a carbonate formation, and the CO₂sensor, by measuring the amount of CO₂ produced, can provide a measureof the effectiveness of that acid deployment. As such, in someembodiments of the present disclosure, a combination sensor may be usedto measure the CO₂ and mineral acid concentrations.

Heater

As mentioned above, the sensor of FIGS. 1A and 1B may comprise a heater8 which is operable to locally heat the window 4, thereby cleaning thesurface of the window in contact with the fluid.

Cleaning the window in this manner is particularly effective, comparedto other techniques such as ultrasonic cleaning or mechanical wipercleaning.

The window 4 can be formed, for example, of diamond (e.g. by chemicalvapour deposition). In some embodiments of the present disclosure, acentral (typically undoped) area of the window can be mid-infraredtransmissive, while an annular encircling area of the window can be madesemiconductive, e.g. by boron doping that part of the window. The heater8 may comprise a simple electrical power source which sends a currentthrough the window to induce resistive heating of the encircling area.The central area of the window is then heated by thermal conduction fromthe encircling area. Boron-doping of diamond components is discussed inU.S. Pat. No. 7,407,566, which is incorporated by reference herein forall purposes.

In some embodiments of the present disclosure, the heater 8 may be ableto heat the window to at least about 400° C. This is higher than the374° C. super-critical point for water, where super-critical water is agood cleaner and oxidiser. In embodiments of the present disclosure, itmay be unnecessary to keep the window at high temperature for a longtime period. In particular, less than a microsecond at peak temperaturemay be enough for cleaning purposes, with longer periods requiring morepower and increasing the risk of overheating of other parts of thesensor.

Pressure Pulse Cleaner

In addition, or as an alternative, to the above heater, cleaning of thewindow 4 may, in some embodiments of the present disclosure, beperformed by providing the sensor with a pressure pulse arrangement. Forexample, the sensor may be located on a fluid flow line between a pumpfor the fluid and an exit port from the flow line. With the exit port ina closed position, the fluid pressure can be increased in front of thewindow to above hydrostatic pressure by the pump. Subsequent of openingthe exit port creates a sudden pressure difference that flushes theflowline fluid, e.g. to the borehole. The sudden movement of dense fluidin front of the window dislodges and carries away window contamination.A 1000 psi (6.9 MPa) pressure pulse is generally sufficient in mostcases.

All references referred to above are hereby incorporated by reference.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the scope of the present disclosure,and that they may make various changes, substitutions and alterationsherein without departing from such scope.

1. A sensor for monitoring a hydrate inhibitor dissolved in a liquid,the sensor comprising: an internal reflection window configured tocontact the liquid in use; a mid-infrared light source configured todirect a beam of mid-infrared radiation into the internal reflectionwindow to provide for attenuated internal reflection at an interfacebetween the internal reflection window and the liquid; a first narrowbandpass filter configured to preferentially transmit mid-infraredradiation over a band of wavelengths corresponding to an absorbance peakof the dissolved hydrate inhibitor to provide for filtering internallyreflected mid-infrared radiation received from the internal reflectionwindow; an infrared detector configured to detect the filteredmid-infrared radiation transmitted through the first filter, wherein thefirst narrow bandpass filter is located in between the internalreflection window and the infrared detector; and a processorarrangement, operably coupled to the infrared detector and configured tomeasure intensity of the detected mid-infrared radiation transmittedthrough the first narrow bandpass filter and determine an amount of thehydrate inhibitor dissolved in the liquid from the measured intensity.2. The sensor according to claim 1, wherein the first narrow bandpassfilter is configured to preferentially transmit mid-infrared radiationover at least one of a band of wavelengths corresponding to: a 1040 cm⁻¹absorbance peak for monoethylene glycol; a 1084 cm⁻¹ absorbance peak formonoethylene glycol; a 1020 cm⁻¹ absorbance peak for methanol; a 1045cm⁻¹ absorbance peak for ethanol; and a 1295 cm⁻¹ absorbance peak forpolyvinylpyrrolidone.
 3. The sensor according to claim 1, furthercomprising: a second narrow bandpass filter in between the internalreflection window and the infrared detector, the second narrow bandpassfilter being configured to transmit mid-infrared radiation over a bandof wavelengths corresponding to a reference portion of the absorbancespectrum of the liquid.
 4. The sensor according to claim 3, furthercomprising: the or a further infrared detector configured to detectfiltered mid-infrared radiation transmitted through the second filter,wherein the processor arrangement is configured to measure a referenceintensity of the detected mid-infrared radiation transmitted through thesecond filter and use the measured reference intensity in thedetermination of the amount of the hydrate inhibitor in the liquid. 5.The sensor according to claim 1, wherein the first narrow bandpassfilter comprises a plurality of the first narrow bandpass filters eachconfigured to transmit mid-infrared radiation over a band of wavelengthscorresponding to an absorbance peak of a respective hydrate inhibitor,and wherein the or a respective further infrared detector is configuredto detect the filtered mid-infrared radiation transmitted through eachof the plurality of the first narrow bandpass filters and the processorarrangement is configured to measure intensity of the detectedmid-infrared radiation transmitted through each first narrow bandpassfilter and determine therefrom an amount of each hydrate inhibitor inthe liquid.
 6. The sensor according to claim 4, wherein the determinedamounts of the hydrate inhibitor in the liquid is in the form of a ratioof the concentrations of the hydrate inhibitors.
 7. The sensor accordingto claim 1, wherein the beam of mid-infrared light is pulsed.
 8. Thesensor according to claim 1, wherein the internal reflection windowcomprises one of a diamond window or a sapphire window.
 9. The sensoraccording to claim 1, further comprising: a heater configured to heatthe internal reflection window.
 10. The sensor according to claim 1,further including: a pressure pulse arrangement configured to produce apressure pulse in the fluid at the internal reflection window to clean asurface of the internal reflection window in contact with the fluid. 11.The sensor according to claim 1, wherein the sensor is located subsea.12. A method of monitoring a hydrate inhibitor dissolved in a liquid,the method including: providing the sensor of claim 1 such that theinternal reflection window is in direct contact with the liquid; andoperating the sensor to determine an amount of the hydrate inhibitordissolved in the liquid.
 13. A well or pipeline tool including thesensor of claim
 1. 14. A method for monitoring a hydrate inhibitordissolved in a liquid, comprising: directing a beam of mid-infraredradiation into an internal reflection window that is in contact with theliquid; passing an attenuated internal reflection of the beam from aninterface between the internal reflection window and the liquid througha narrow bandpass filter configured to preferentially transmitmid-infrared radiation over a band of wavelengths corresponding to anabsorbance peak of the dissolved hydrate inhibitor; detecting thefiltered mid-infrared radiation transmitted through the first filter;measuring an intensity of the detected mid-infrared radiationtransmitted through the first filter; and determining an amount of thehydrate inhibitor dissolved in the liquid from the measured intensity.15. The method according to claim 14, wherein the narrow bandpass filteris configured to preferentially transmit mid-infrared radiation over atleast one of a band of wavelengths corresponding to: a 1040 cm⁻¹absorbance peak for monoethylene glycol; a 1084 cm⁻¹ absorbance peak formonoethylene glycol; a 1020 cm⁻¹ absorbance peak for methanol; a 1045cm⁻¹ absorbance peak for ethanol; and a 1295 cm⁻¹ absorbance peak forpolyvinylpyrrolidone.
 16. The method according to claim 14, furthercomprising: passing the attenuated internal reflection of the beam fromthe interface between the internal reflection window and the liquidthrough a reference narrow bandpass filter configured to transmitmid-infrared radiation over a band of wavelengths corresponding to areference portion of the absorbance spectrum of the liquid.
 17. Themethod according to claim 16, further comprising: detecting a portion ofthe attenuated internal reflection of the beam from the interfacebetween the internal reflection window and the liquid transmittedthrough the reference filter; measuring a reference intensity of theportion of the attenuated internal reflection of the beam from theinterface between the internal reflection window and the liquidtransmitted through the reference filter; and using the measuredreference intensity in the determination of the amount of the hydrateinhibitor in the liquid.